Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: June 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(40), P. 7434 - 7439
Published: Oct. 3, 2022
Aryl
borates
lie
at
the
heart
of
carbon–carbon
bond
couplings,
and
they
are
widely
applied
to
synthesis
functional
materials,
pharmaceutical
compounds,
natural
products.
Currently,
synthetic
methods
for
aryl
mostly
limited
metal-catalyzed
routes,
nonmetallic
strategies
remain
comparatively
underdeveloped.
Herein,
we
report
a
mild,
scalable,
visible-light-induced
cross-coupling
between
dibenzothiophenium
triflate
salts
bis(catecholato)-diboron
construction
C–B
bonds
in
absence
base,
transition
metal–ligand
complex,
or
photoredox
catalyst.
Mechanistic
studies
reveal
that
this
transformation
is
achieved
through
an
electron
donor–acceptor
(EDA)
complex
activation
The
mild
reaction
conditions
allow
preparation
aromatic
good
yields
with
excellent
group
tolerance.
This
photochemical
protocol
was
also
successfully
late-stage
modification
products
drug
intermediate,
greatly
demonstrating
broadened
utility.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4786 - 4827
Published: Jan. 1, 2024
This
review
summarizes
structural
and
synthetic
aspects
of
heterocyclic
molecules
incorporating
an
atom
a
hypervalent
main-group
element.
The
higher
thermal
stability
heterocycles,
as
compared
to
their
acyclic
analogs,
adds
special
feature
chemistry.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(20), P. 13689 - 13696
Published: May 13, 2024
A
detailed
mechanistic
study
of
the
Z-selective
allylic
functionalization
via
thianthrenium
salts
is
presented.
Kinetic
analyses,
deuterium
labeling
experiments,
and
computational
methods
are
used
to
rationalize
observed
reactivity
selectivity.
We
find
that
reaction
proceeds
a
rate-determining
stereodetermining
deprotonation
an
alkenylthianthrenium
species.
The
Z-configuration
resultant
ylide
translated
into
Z-allylic
amine
product
through
sequence
subsequent
fast
irreversible
steps:
protonation
form
electrophile
then
regioselective
substitution
by
nucleophile.
In
step,
studies
identified
series
stabilizing
nonbonding
interactions
in
Z-alkene-forming
transition
state
contribute
stereoselectivity.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: June 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
